Production of color lakes



.25 other necessarycomponents. For" example,

Patented June 6, 1933 UNITED s'ri vriz sv PATENT OFFICE Bono'zsoHrMMEmoF LUnwIGsHArnN oiv-rHE-nrrrN GERMANY, ASSIGNOR To to.

FARBENINDUSTBIE AKTIENGESELLSGHAFT, :OF

Pnonuo rroiv or COLOR LAKES No Drawing.

Original application filed November l, 1 928, Seri'alNo. 316,625, and in Germany November 14, 1927. Divided and'this application men m '11, 1931. .seriai No. 536,657.

The present invention relates to the *production of complex -compoundscontaining tungsten or molybdenum or both and color lakes obtained therewith. v I s It is already known'that' valuablecomplex compounds can be produced from compounds of tungsten or molybdenum, or both, by treating "the latter with compounds of phosphorus, silicon, boron, aluminium, chromium, iron, manganese, arsenic, antimony and the like.

I have now found that other valuable complex compounds containing tungsten or molybdenum, or both, can be produced by mixing together the dissolved substances requisite for-the production of the said valuable complex compounds, and'bringing reducing agents into action simultaneously or subsequently, or by employing the components containing the tungsten or molybdenum compounds in a lowstage of oxidation, as for example by treating 'tungstates or molybdates with reducing agents, and then subjecting them to the action of the reducing agents, such as a solution of a bisulphite, hydrosulphite, dextrose and the like may be allowed to act on mixtures of sodium tungstate'and sodium molybdate' or of sodium silicate or borate and sodium molybdate, and, under these conditions, generally deep violetblue solutions, containing the new complex compounds,*are produced. It is advantageous to carry out the operation in the presence of inorganic or organic acids,

' and it is also sometimes suitable to work under pressure. The complex compounds may be recovered in the dry state by-salting out their solutions, or by passing gaseous hydrochloric acid therethrough, or by evaporating their solutions;

Again, phosphotungstic acid, or salts of the same, may be treated with molybdenum salts and phosphates, the resulting product being then reduced. The tungsten or molyb-' denum compounds may also be reduced in the first instanceand the resulting products may be subjected'to the action of'compounds capable of producing complex compounds containing tungsten or molybdenum.

rnANKFon' oN-THE-MMN, 153- v The new complex compounds produced as duction of these complex compounds, con- I taining molybdenum or tungsten or both, may also be combined with the preparation of the color lakes or. pigments, as for example by adding the basic dyestufl', at the time of niixi-ngthe components, required for the formation of the complex compounds, to-- gether with the reducing agent.- i p The preparation of the aforesaid color lakes i'spreferably carried out in solution, most suitably in aqueous solution. The ope erati'onmay be performed under ordinary pressure, but it is often advantageous .to

subject the color lakes to pressure at an elevated temperature, which, however, should i not be-so high'that the color lakes are decomposed ordestroyed-during or after their production.

The color lakes may also be produced in the presence of the substrata usually employed in the color lakeindustry, such as tor instance heavy spar, hydrated aluminium oxide,'or a mixture of the latter with blanc.

fixe and the like, and the process may becarried out with the addition of dispersive agents, such as'salts of alkylated naphthalene sulphonic acids, sodium cholate, Turkey red'oils and the like.

I Thefollowing examples will further illustrate the nature of the said invention which, however, is not limited thereto. The

parts are by weight where not otherwise specified,

' Example 1 80'parts of sodium tungstate dissolved in -,water (1:5) are mixed with the aqueous solutions (1-: 10) of 15 parts of disodium phosphate and 40 parts of sodium molybdate,

80 parts by volume of hydrochloric acid (20 Baum) being added. 5 parts of powdered hydrosulphite are introduced, and the charge, after standing for a time, is slowly heated to boiling. Boiling is continued until the smell of sulphuretted hydrogen has disappeared, the mixture being then cooled and made up to 1000 parts by volume.

The hydrosulphite may be replaced by 20 parts of 38 Baum sodium bisulphite solution.

The complex compound can be easily precipitated, in the solid form, for example by passing gaseous hydrochloric acid through the solution obtained according to the example.

The solution obtained in this manner, or the complex phosphotungstomolybdenum compound isolated therefrom is used for precipitating basic dyestuiis, and furnishes color lakes which are substantially faster to light than those obtained by using the corresponding phosphotungstomolybdenum compounds prepared without the employment of reducing agents.

Ewdmple 2 An aqueous solution (1: 20) of 18 parts of calcined soda is added at about 7 0 C. to an aqueous solution (1 20) of 37 parts of aluminium sulphate and the precipitated hydrated aluminium oxide washed as usual. 6 parts of, Diamond green G (Color Index 1924 No. 66-2) dissolved in 600 parts of water are addtothe hydrated aluminium oxide substratuin and precipitated by the addition of 100 parts by volume of the solution of the reduced complex salt obtained according to Exampl'e '1.

The color lake thus obtained when worked to a wall paper'dye furnishes bright green shades of a high fastness to light.

Example 3 Example 4 12 parts of p-aminobenzaldehyde are dissolved in 2000 parts of hot Water after the addition of 25 parts of hydrochloric acid of 20 Baum, The said solution is stirred into 600 parts by volume of the solution of the reduced complex salt obtained according to Example 1. orangepigment of very good fastiiess to light is obtained.

I This application has been divided out from my copending application Ser. No. 316,625, filed November 1, 1928.

What I claiin is:

1. A processof producing color lakes and pigments, which comprises treating an or- -gani'c compound selected from the group con sisting of basic dyestuiis which may also contain acid groups, and aromatic amines de-' 7 void of affinity tonatural fibres and free from acid groups, with a complex compound obtainable by acting on a soluble compound ofat least one metal selected from the group consisting of tungsten and molybdenum, with a reducing agentand an acid derived from an element selected from the group con.- si'sting of iron, phosphorus, silicon, manganese, boron, arsenic and antimony or a salt ofsuch an acid. 1

2.- A process of producing color lakes, 9,)

which comprises treating a basic dyestufi with a complex compound obtainable by acting on a soluble compound of .at least one metal selected from the group consisting of tungsten and molybdenum with a reducing agent and an acid derived froman element selected from thegroup consistingof iron, phosphorus, silicon, manganese, boron, arsenic and antimony ,or a salt of such an acid.

, 3. A process of producing color lakes, which fcomprises treating a basic dyestuii' with a complex compound obtainable by acting on an acid solution containing a molybdate and an acid derived from an element selected from the groupcon sisting of iron, 1

phosphorus, silicon, manganese, boron, arsenic and antimony or a salt of su'ch an acid with a reducing agent. I n 4, A process of producing color lakes, which comprises treating a basic dyestuff 1 with a complex compound obtainable byacting onan acid solution containing a molybdate and a phosphate with a reducing agent.

5., As 'new jarticles of manufacture pigments containing in complex combination a fcompoundof at least'one of the metals tungsten and molybdenum in a 10W stage of oxidation, which pigments are obtainable by treating' an aromaticamine, devoid of any affin ity to natural fibres and free from acid groups, with a complex compound which contains at least one of the said metals and which obtainable by acting on a soluble compoundof at least one of the said metals with a reducing agent and an acid derived from an element'selected from the groupcon- 'sisting of iron, phosphorus, silicon, manganese, boron, arsenic and antimony or a salt of such an acid. v

6. A process of producing color lakes which comprises treating a basic dyestufl with a complex compound obtainable by acting on an acid solution containingsodium molybdate and a sodium phosphate with a reducing agent. V I

" 7. A process of producing color lakes which comprises treating a basic dyestufi with a complex compound obtainable by acting on an acid solution containing sodium molybdate and disodium phosphate with a reducing agent. s

8. A process of producing color lakes which comprises treating a basis dyestuif with a complex compound obtainable by acting on an acid solution containing sodium tungstate, sodium molybdate and disodium phosphate with sodium hydrosulfite. In testimony whereof I afiix my signa-' ture.

BODO ZSCHIMMER. 

